WO2020099290A1 - Revêtement facile à nettoyer - Google Patents

Revêtement facile à nettoyer Download PDF

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Publication number
WO2020099290A1
WO2020099290A1 PCT/EP2019/080795 EP2019080795W WO2020099290A1 WO 2020099290 A1 WO2020099290 A1 WO 2020099290A1 EP 2019080795 W EP2019080795 W EP 2019080795W WO 2020099290 A1 WO2020099290 A1 WO 2020099290A1
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WIPO (PCT)
Prior art keywords
precursor composition
organyl
coating
independently selected
solution
Prior art date
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PCT/EP2019/080795
Other languages
English (en)
Inventor
Mi Zhou
Neil Gregory Pschirer
Hsin Tsao TANG
Ying Jung Chen
Sami PIRINEN
Ari Karkkainen
Milja Hannu-Kuure
Oskari MAEKIMARTTI
Original Assignee
Basf Se
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Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to EP19798104.6A priority Critical patent/EP3880371A1/fr
Priority to CN201980074374.9A priority patent/CN113015581A/zh
Priority to KR1020217017637A priority patent/KR20210090670A/ko
Priority to US17/293,665 priority patent/US20220010170A1/en
Priority to JP2021525814A priority patent/JP2022507316A/ja
Publication of WO2020099290A1 publication Critical patent/WO2020099290A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups

Definitions

  • the present invention relates to a process for preparing coatings which have high hardness and are abrasion resistant and easy to clean, a coating composition, an article comprising the coating and the use for the coating composition for preparing a coating.
  • E2C Easy- to-clean
  • siloxane functionalized perfluoropolyether which has been shown to give good E2C properties along with abrasion resistance.
  • these types of materials can typically use only certain types of solvents, namely fluorosolvents, for dilution which makes these materials highly expensive along with the production costs. Even in case a complete avoidance of fluorosolvents may not be possible, at least a reduction of the amount of fluorosolvents needed is, thus, desirable, e.g. by using mixtures of fluorosolvents with non-fluorosolvents.
  • these types of materials are typically used to produce monolayer coatings.
  • the monolayer coating in principle mimic the hardness of the underlying substrate.
  • Such monolayer coatings typically suffer also from poor long-term thermal stability especially when exposed to high temperatures, especially when exposed to humidity. Moreover, these monolayer coatings cannot pass severe abrasion resistance conditions and retain long term use life.
  • coatings are required with excellent E2C properties, high hardness and high durability which can maintain these properties over abrasion and environmental conditions.
  • Such coatings should be usable on both smooth and rough substrate surfaces and on different types of substrates such as glass, ceramic, and/or metal.
  • an improvement of the hardness of the surface the coating is applied to is desirable.
  • this should be achieved by using single layer film on the substrate without the need of specific additional primer layers.
  • the coating compositions should be applicable by liquid phase deposition in atmospheric conditions by using slot, spin, spray, bar, roller or other typical coating method to produce the wet film and should be curable at relatively low final curing temperatures, e.g. 150 to 250°C or even at 80°C.
  • relatively low final curing temperatures e.g. 150 to 250°C or even at 80°C.
  • costly and cumbersome processes such as e- beam or plasma enhanced chemical vapor deposition (PECVD) should be avoided.
  • a process for preparing a thin film on a substrate comprising the steps of
  • M 1 is a metal or metalloid with a valence z
  • R 1 is each independently selected from a Ci to Cio organyl or organoheteryl group
  • R 2 is each independently selected from a Ci to C20 organyl, organoheteryl,
  • n 1 to z
  • m z-1 to 0
  • n+m is z a2) at least partial hydrolysation of the M 1 (OR 1 )-moieties and polymerizing the one or more metal or metalloid compound according to formula (I); b) preparing a second precursor composition (SPC) in a second vessel, the
  • composition (SPC) composition (SPC);
  • step d) optionally partially or completely removing solvent, if present, after step d);
  • step f) curing the intermediate product obtained in step e), if present, or step d), if step e) is not present thereby obtaining a thin film.
  • the thus obtained coatings provide superior hardness, abrasion resistance and excellent surface cleanability.
  • the coating can further enhance the optical properties of display device. Furthermore, the usage of an excess of fluorine containing solvents can be avoided and applicability with wider deposition equipment range is achieved.
  • the composition can be applied by conventional methods and cured at low temperature. The composition provides improved adhesion without the need of using additional adhesion promotion layers for multiple substrate surfaces. It has also superior thermal and long-term performance stability (meaning use life stability as a thicker physical coating rather than thin monolayer on substrate) and is cost effective due to lower fluorine solvent content and fluorine content. Detailed description of the invention
  • An organyl group is an organic substituent group, having one free valence at a carbon atom.
  • An organoheteryl group is an organic substituent group, having one free valence at an atom different from a carbon atom.
  • a fluorinated organyl group or fluorinated organoheteryl group is an organyl group or organoheteryl group as defined above, in which at least one hydrogen atom is replaced by fluorine.
  • the first precursor composition is prepared in a first vessel, the preparation comprising the following steps:
  • M 1 is a metal or metalloid with a valence z
  • R 1 is each independently selected from a Ci to C10 organyl or organoheteryl group
  • R 2 is each independently selected from a Ci to C20 organyl, organoheteryl,
  • n 1 to z
  • m z-1 to 0
  • n+m is z a2) at least partial hydrolysation of the M 1 (OR 1 )-moieties and polymerizing the one or more metal or metalloid compound according to formula (I);
  • step a1) up to five different metal or metalloid compounds according to the formula (I) may be provided, usually, not more than three different metal or metalloid compounds according to the formula (I) are provided.
  • the one or more metal or metalloid compound(s) according to formula (I) is/are free from fluorine.
  • the one or more metal or metalloid compound(s) according to formula (I) is/are free from fluorine.
  • more than one metal or metalloid compound(s) according to formula (I) is/are free from fluorine.
  • no fluorine containing compound except optionally fluorine containing solvents is/are present during the preparation of the first precursor composition (FPC) before step c) is accomplished, even more preferably, in case solvents are present, the amount of fluorine- containing solvents based on the total weight of the solvents present is equal or less than 75 weight % is present and most preferably no fluorine containing compound including fluorine containing solvents are present during the preparation of the first precursor composition (FPC) before step c) is accomplished.
  • one or more of the one or more metal or metalloid compound(s) according to formula (I) comprise at least one fluorine atom in the R 2 residue of formula (I).
  • one or more, such as 1 , 2 or three metal or metalloid compound(s) according to formula (I) contain one or more fluorine atoms in the R 2 residue of formula (I).
  • M 1 is preferably selected from Si, Ge, Sb, Ti, Zr, Al, Sn, W, Se, Cr, Ag or Ni, more preferably from Si, Ti, Zr, Ge, Sb, and most preferably M 1 is Si.
  • R 1 is each independently selected from a Ci to Cio organyl or organoheteryl group.
  • heteroatoms are present in the organyl group of R 1 they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • Preferred groups OR 1 are alkoxy, acyloxy and aryloxy groups.
  • the heteroatom of the organoheteryl group of R 1 bound to the oxygen atom bound to M 1 is usually different from O.
  • heteroatom(s) present in the organoheteryl group of R 1 are preferably selected from N, O,
  • P or S more preferably selected from N and O.
  • the total number of heteroatoms, if present, in R 1 is usually not more than five, preferably not more than three.
  • R 1 is a Ci to Cio organyl group containing not more than three heteroatoms, more preferably R 1 is a Ci to Cio hydrocarbyl group, even more preferably a Ci to Cio linear, branched or cyclic alkyl group.
  • the total number of carbon atoms present in R 1 according to any one of the above variants is 1 to 6, more preferably 1 to 4.
  • R 2 is each independently selected from a Ci to C20 organyl or organoheteryl group in the first embodiment or is each independently selected from a Ci to C20 organyl, organoheteryl fluorinated organyl or fluorinated organoheteryl group in the second embodiment.
  • heteroatoms are present in the organyl group of R 2 they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • the heteroatom of the organoheteryl group of R 2 bound to M 1 is usually different from O.
  • heteroatom(s) present in the organoheteryl group of R 2 are preferably selected from N, O,
  • P or S more preferably selected from N and O.
  • the total number of heteroatoms, if present, in R 2 is usually not more than eight, preferably not more than five and most preferably not more than three.
  • R 2 is a Ci to C20 organyl group containing not more than three heteroatoms, more preferably R 2 is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.
  • R 2 is a Ci to C20 organyl group and/or fluorinated organyl groups containing not more than three heteroatoms, more preferably R 2 is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.
  • the fluorinated organyl groups preferably comprises from 1 to 30 fluorine atoms, more preferably from 3 to 17 fluorine atoms.
  • the total number of carbon atoms present in R 2 according to any one of the above variants is 1 to 15, more preferably 1 to 12 and most preferably 1 to 10.
  • n is at least 2. In case the valence z of the metal or metalloid M 1 is 4 or more, n is preferably at least 3.
  • each R 1 and R 2 are the same. Hence, R 1 and R 2 may still be different.
  • each respective R 1 and R 2 are the same.
  • R 1 of one compound according to formula (I) may still be different from R 1 of another compound according to formula (I).
  • Suitable compounds accordinging to formula (I) are, for example triethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyl- diethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-butyltriethoxysilane,
  • vinyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, aminopropyltrimethoxysilane, n-hexyltrimethoxysilane, propyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane,
  • methacryloxypropylmethyldiethoxysilane mercaptpropyltrimethoxysilane, mercaptpropyl methyldimethoxysilane, acryloxypropyltrimethoxysilane, allyltrimethoxysilane,
  • MTMOS methyltrimethoxysilane
  • MTEOS methyltriethoxysilane
  • DMDEOS dimethyldiethoxysilane
  • PTEOS phenyl triethoxysilane
  • step a2) the M 1 (OR 1 )-moieties can be at least partially hydrolysed in the presence of a compound according to the following formula (II) may be present
  • M 2 , M 2’ are the same or different and are each independently selected from a metal or metalloid with a valence x;
  • Y is a divalent linking group
  • R 6 , R 6’ are the same or different and are each independently selected from a Ci to Cm organyl or organoheteryl group;
  • R 7 , R 7’ are the same or different and are each independently selected from a Ci to C20 organyl or organoheteryl group;
  • s, s’ are the same or different and are each independently selected from 1 to x-1 ; t, t’ are the same or different and are each independently selected from is x-2 to 0; s+t is x-1 ; and
  • s’+t’ is x-1.
  • step a2) a compound according to formula (II) is present, this compound is preferably provided in a further step a1 a) which may be accomplished before, after or together with step a1).
  • M 2 and M 2’ are preferably independently selected from Si, Ge, Sb, Ti, Zr, Al, Sn, W, Se, Cr, Ag or Ni, more preferably independently selected from Si, Ti, Zr, Ge, Sb, and most preferably M 2 and M 2’ are Si.
  • M 2 and M 2’ are the same.
  • Y preferably is selected from a Ci to C 20 organyl or organoheteryl group, more preferably is selected from a Ci to C 20 hydrocarbyl group, even more preferably is selected from a Ci to C 20 linear or branched or cyclic alkyl group or a C6 to C 20 aryl group.
  • R 6 , R 6’ are the same or different and are each independently selected from a Ci to C 10 organyl or organoheteryl group.
  • heteroatoms are present in the organyl group of R 6 and/or R 6’ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • OR 6 and/or OR 6’ are alkoxy, acyloxy and aryloxy groups.
  • the heteroatom of the organoheteryl group of R 6 and/or R 6’ bound to the oxygen atom bound to M 1 is usually different from O.
  • heteroatom(s) present in the organoheteryl group of R 6 and/or R 6’ are preferably selected from N, O, P or S, more preferably selected from N and O.
  • the total number of heteroatoms, if present, in R 6 and/or R 6’ is usually not more than five, preferably not more than three.
  • R 6 and/or R 6’ is a Ci to C 10 organyl group containing not more than three
  • R 6 and/or R 6’ is a Ci to C 10 hydrocarbyl group, even more preferably a Ci to C 10 linear, branched or cyclic alkyl group.
  • the total number of carbon atoms present in R 6 and/or R 6’ according to any one of the above variants is 1 to 6, more preferably 1 to 4.
  • R 6 and R 6’ are the same.
  • R 7 , R 7’ is each independently selected from a Ci to C 20 organyl or organoheteryl group.
  • heteroatoms are present in the organyl group of R 7 and/or R 7’ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • the heteroatom of the organoheteryl group of R 7 and/or R 7’ bound to M 1 is usually different from O.
  • the heteroatom(s) present in the organoheteryl group of R 7 and/or R 7’ are preferably selected from N, O, P or S, more preferably selected from N and O.
  • the total number of heteroatoms, if present, in R 7 and/or R 7’ is usually not more than eight, preferably not more than five and most preferably not more than three.
  • R 7 and/or R 7’ is a Ci to C20 organyl group containing not more than three
  • R 7 and/or R 7’ is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.
  • the total number of carbon atoms present in R 7 and/or R 7’ according to any one of the above variants is 1 to 15, more preferably 1 to 10 and most preferably 1 to 6.
  • R 7 and R 7’ are the same.
  • s and/or s’ is at least 2. In case the valence z of the metal or metalloid M 2 and/or M 2’ is 4 or more, s and/or s’ is preferably at least 3.
  • Suitable compounds according to formula (II) are, for example 1 ,2-bis(trimethoxysilyl)methane,
  • the at least partial hydrolysation in step a2) is preferably accomplished under acidic or basic conditions, usually using a catalyst, such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid or another mineral or organic acid or a base, more preferably a mineral acid such as HNO 3 .
  • a catalyst such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid or another mineral or organic acid or a base, more preferably a mineral acid such as HNO 3 .
  • the concentration of the acid is preferably 0.01 mol/l to 1.0 mol/l, more preferably 0.05 mol/l to 0.2 mol/l.
  • the acid is usually dissolved in water or in a mixture of water and an organic solvent, e.g. an alcohol, a ketone, preferably a ketone, such as acetone.
  • the at least partial hydrolysation in step a2) is preferably accomplished at a temperature between 50 and 150°C, more preferably 80 - 120°C.
  • the at least partial hydrolysation in step a2) is preferably accomplished for 0.5 to 10 hours, preferably 1.0 to 5.0 hours.
  • a basic substance e.g. an amine, such as a Ci to C4-trialkylamine may be added.
  • the molecular weight of the product of step a2) is 500 g/mol to 6000 g/mol, more preferably 800 g/mol to 4000 g/mol.
  • one or more additional organic solvents may be used.
  • the solvent(s) is/are selected from alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as
  • ketones such as acetone
  • esters such as
  • propyleneglycolmonomethyletheracetate ethyl acetate, methylformate and ethers, such as diethyl ether, THF, preferably alcohols, ether alcohols or ketones
  • a mixture of up to five organic solvents may be used, preferably not more than three organic solvents are used and most preferable only one organic solvent is used.
  • the organic solvent(s) used during the preparation of the first precursor composition is fluorine free.
  • step a3) in case a solvent is present in step a2) exchanging the solvent or solvents used in step a2) by one or more organic solvents as outlined above,
  • step a2) adding one or more organic solvents as outlined above.
  • Exchanging the solvents denotes that the solvent or solvent mixture present before and after the solvent exchange are different. Usually, at least the water present in the at least partial hydrolysation in step a2) is removed by the solvent exchange.
  • the water and optionally organic solvent, e.g. ketone, used in the at least partial hydrolysation in step a2) is/are replaced by a different organic solvent, e.g. alcohol, such as ether alcohol.
  • a different organic solvent e.g. alcohol, such as ether alcohol.
  • the solids content of the first precursor composition is preferably 1.0 to 25 wt.% based on the entire first precursor composition, more preferably 5 to 20 wt.% based on the entire first precursor composition.
  • the preparation of the first precursor composition is preferably accomplished within a temperature range of 0 to 150°C, more preferably within a temperature range of 40 to 120°C.
  • the second precursor composition is prepared in a second vessel, the preparation comprising the following step:
  • the fluoropolyether silane comprising hydrolysable groups is preferably selected from compounds according to the following formula (III)
  • R F is a fluoropolyether group
  • Q is a divalent linking group
  • R 3 is each independently selected from a Ci to Cio organyl or organoheteryl group
  • R 4 is each independently selected from a Ci to C20 organyl or organoheteryl group
  • o 1 , 2 or 3
  • p 0, 1 or 2
  • R 5 is H, C X F2 X+I with x being 1 to 10 or -Q-Si(OR 3 ) 0 R 4 p , with Q, R 3 , R 4 , o and p as defined above, whereby in each occurrence Q, R 3 , R 4 , o and p being present may be the same or different.
  • R 3 is each independently selected from a Ci to C10 organyl or organoheteryl group.
  • heteroatoms are present in the organyl group of R 3 they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • Preferred groups OR 3 are alkoxy, acyloxy and aryloxy groups.
  • the heteroatom of the organoheteryl group of R 3 bound to the oxygen atom bound to M 1 is usually different from O.
  • heteroatom(s) present in the organoheteryl group of R 3 are preferably selected from N, O,
  • P or S more preferably selected from N and O.
  • R 3 The total number of heteroatoms, if present, in R 3 is usually not more than five, preferably not more than three.
  • R 3 is a Ci to Cio organyl group containing not more than three heteroatoms, more preferably R 3 is a Ci to Cm hydrocarbyl group, even more preferably a Ci to Cm linear, branched or cyclic alkyl group.
  • the total number of carbon atoms present in R 3 according to any one of the above variants is 1 to 6, more preferably 1 to 4.
  • R 4 is each independently selected from a Ci to C20 organyl or organoheteryl group
  • heteroatoms are present in the organyl group of R 4 they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • the heteroatom of the organoheteryl group of R 4 bound to Si is usually different from O.
  • the heteroatom(s) present in the organoheteryl group of R 4 are preferably selected from N, O, P or S, more preferably selected from N and O.
  • the total number of heteroatoms, if present, in R 4 is usually not more than eight, preferably not more than five and most preferably not more than three.
  • R 4 is a Ci to C20 organyl group containing not more than three heteroatoms, more preferably R 4 is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.
  • the total number of carbon atoms present in R 4 according to any one of the above variants is 1 to 15, more preferably 1 to 10 and most preferably 1 to 6.
  • o is preferably 1 to 3, more preferably 2 or 3 and most preferably 3
  • p is preferably 0 to 2, more preferably 0 or 1 and most preferably 0.
  • the fluoropolyether group R F usually has a molecular weight of 150 to 10,000 g/mol, more preferably 250 to 5,000 g/mol and most preferably 350 to 2,500 g/mol.
  • fluorine/hydrogen is preferably at least 5, more preferably at least 10. More preferably, the fluoropolyether group R F is a perfluoropolyether group.
  • the fluoropolyether group R F may be a linear or branched group, preferably is a linear group.
  • the repeating units of the fluoropolyether group R F are preferably Ci to C 6 fluorinated dialcohols, more preferably Ci to C4 fluorinated dialcohols and most preferably Ci to C3 fluorinated dialcohols.
  • Preferable monomers of the fluoropolyether group R F are perfluoro-1 ,2-propylene glycol, perfluoro-1 ,3-propylene glycol, perfluoro-1 ,2-ethylene glycol and difluoro-1 ,1 -dihydroxy- methane, preferably perfluoro-1 ,3-propylene glycol, perfluoro-1 ,2-ethylene glycol and difluoro- methanediol.
  • the latter monomer, difluoro-1 ,1 -dihydroxy-methane, may be obtained by oxidizing
  • Preferred structures for a divalent perfluoropolyether group include
  • Preferred structures for a monovalent perfluoropolyether group include
  • fluoropolyether groups R F are selected from
  • R-[CsF 6 0] n - with n 2 to 10 and R being a linear or branched, preferably linear, perfluorinated C2 or C3-alcohol, preferably C3-alcohol;
  • the divalent linking group Q links the perfluorpolyether with the silicon-containing group.
  • Q is usually having a molecular weight of not more than 500 g/mol, more preferably not more than 250 g/mol and most preferably not more than 150 g/mol.
  • divalent linking groups are amide-containing groups and alkylene groups.
  • Fluoropolyether silane compounds comprising hydrolysable groups can be commercially available without public knowledge of their exact chemical structure.
  • Suitable commercially available fluoropolyether silane comprising hydrolysable groups are, for example Fluorolink S10 (CAS no. 223557-70-8, Solvay), OptoolTM DSX (Daikin Industries), Shin-Etsu SubelynTM KY-1900 (Shin-Etsu Chemical) and Dow Corning ® 2634 (CAS no. 870998- 78-0).
  • organic solvents may be used.
  • the solvent(s) is/are selected from alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as
  • propyleneglycolmonomethylether ethylene glycol, ketones, esters, such as ethyl acetate, methylformate, ethers, such as partially or completely fluorinated ethers, partially or completely fluorinated hydrocarbons, particularly preferred are alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as
  • propyleneglycolmonomethylether partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof
  • ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, e.g. methoxy- nonafluorobutane, methyl-nonaflurobutylether, methyl-nonafluoroisobutylether, ethoxy- nonafluorobutane, isopropyl alcohol, ethanol, propyleneglycolmonomethylether and/or ethylene glycol.
  • the amount of fluorine-containing solvents based on the total weight of the solvents present is equal or less than 90 wt.%, more preferably equal or less than 80 wt.%, and most preferably equal or less than 75 vol.%.
  • Suitable fluorine-containing solvents are, for example, partially or completely fluorinated hydrocarbons, partially or completely fluorinated ethers or mixtures thereof e.g. methyl- nonafluorobutylether, methyl-nonafluoroisobutylether and ethoxy-nonafluorobutane.
  • the solids content of the second precursor composition is preferably 0.2 to 100 wt.% based on the entire first precursor composition, more preferably 0.3 to 20 wt.% based on the entire second precursor composition.
  • the preparation of the second precursor composition is preferably accomplished within a temperature range of 0 to 75°C, more preferably within a temperature range of 20 to 50°C.
  • Step c) During step c) the first precursor composition (FPC) is combined with the second precursor composition (SPC).
  • the combination of the first precursor composition (FPC) and the second precursor composition (SPC) is conducted by mixing the two compositions.
  • the first precursor composition (FPC) and the second precursor composition (SPC) are preferably combined, such as mixed, by adding the two compositions into a vessel, such as a flask, and stirring the combined compositions.
  • the second precursor composition silane groups react with the first precursor composition silane groups to form a pre-polymer ready for coating deposition.
  • Additional organic solvents may be added during step c) in order to obtain the desired final solids content.
  • the amount of fluorine-containing solvents used in the final formulation is equal or less than 90 wt.%, more preferably equal or less than 80 wt.%, and most preferably equal or less than 75 vol.%.
  • the solvent(s) which may be added are selected from alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, ethylene glycol, ketones, esters, such as ethyl acetate, methylformate, ethers, such as partially or completely fluorinated ethers, , particularly preferred are alcohols, preferably containing 1 to 6 carbon atoms, e.g.
  • ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, most preferred are ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, e.g.
  • methoxy-nonafluorobutane methyl-nonaflurobutylether, methyl- nonafluoroisobutylether, ethoxy-nonafluorobutane, ethylacetate, n-hexane, n-pentane, isopropyl alcohol, ethanol, butanol, propyleneglycolmonomethylether, propylene glycol.
  • step c) the weight ratio between the solids contents of the first precursor composition (FPC) and the solids content of the second precursor composition (SPC) is preferably between 100:1.0 to 0.5:1.0, preferably between 80:1.0 to 1.0:1.0, more preferably between 60:1.0 to 1.5:1.0.
  • usual additives used for coating compositions for thin films may be added during step c).
  • Such usual additives include, for example, surfactants, levelling agents, processing aids, antistatic agents, antioxidants, water and oxygen scavengers, catalysts, photoinitators or mixtures thereof.
  • scatter particles usually provide additional optical effects, e.g. to meet specific requirements, such as for lighting applications.
  • These particles can be, for example Si02, Ti02, Zr02, or similar inorganic particles.
  • the solids content of the composition obtained after step c) is preferably 0.1 to 10 wt.% based on the entire composition, more preferably 0.1 to 5 wt.% based on the entire composition.
  • the fluorine content of the solids content of the composition obtained after step c) is 0.005 to 0.3 wt.%, preferably between 0.01 to 0.1 wt.% based on the total formulation composition obtained after step c).
  • the fluorine content of the solids content of the composition obtained after step c) is 0.1 to 17.5 wt.%, preferably between 0.2 to 15 wt.% based on the total solids content of the composition obtained after step c).
  • step c) Usually and preferably the solids content after step c) remains unchanged until step d) is accomplished.
  • the temperature during step c) preferably does not exceed 75°C, more preferably does not exceed 50°C and is usually below 35°C.
  • the reaction time is usually below 24h, preferably 6 to 15 hours.
  • step d a thin layer on the substrate is formed.
  • Suitable substrates include ceramics, glass, metals, natural and man-made stone, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), paints (such as those on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), wood and fibrous substrates (such as textile, leather, carpet, paper).
  • polymeric materials such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate
  • paints such as those on acrylic resins
  • powder coatings such as polyurethane or hybrid powder coatings
  • wood and fibrous substrates such as textile, leather, carpet, paper.
  • the substrate is selected from ceramics, glass, metals, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), natural and man-made stone, more preferably from metals, ceramics, glass and polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate).
  • polymeric materials such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate.
  • Step d) is preferably effected by dip coating, slot coating, combined slot+spin coating, spin coating, spray coating, ink-jet printing, curtain coating, roller coating, roll-to-roll coating, screen printing or using a bar, a brush or by rubbing, more preferably by spray coating, slot coating, dip coating, spin coating, most preferably spray coating and spin coating (to mention few typical liquid phase deposition methods but not limited to these). Such methods are known in the art.
  • the temperature during step d) preferably does not exceed 75°C, more preferably does not exceed 50°C and most preferably does not exceed 35°C.
  • the temperature of the substrate during step d) preferably does not exceed 100°C, more preferably does not exceed 50°C and most preferably does not exceed 35°C. In some cases, it might be preferable to make deposition on pre-heated substrate.
  • a pattern can be formed into the thin film to form surface structures and patterns.
  • Suitable methods for pattern forming are nano-imprinting, embossing, roll-to-roll, gravure, flexo-graphic, roller, ink-jet, screen-printing, spray and or UV lithography is used as patterning process) is used the form surface structures (nano-scale or micro or millimeter scale).
  • the purpose of the pattern forming is to produce additional optical, physical or chemical properties to the thin film.
  • step e) the solvent(s) are preferably partially or completely removed.
  • Step e) is optional and not typically necessary. There are differences between the deposition method and manufacturing line specifications.
  • vacuum dry step can be optionally applied to promote the evaporation of the solvent(s). If vacuum dry step is used, typically it is applied first and followed by the thermal pre-cure. Usually the removal is accomplished at a pressure of 50 to 200 kPa and/or followed by thermal cure at a temperature of 50 to 150 °C, preferably the removal is accomplished at a pressure of 90 to 115 kPa and/or followed by thermal cure at a temperature of 60 to 100 °C.
  • the optional thermal pre-cure is usually effected by exposure to heat, e.g. by using a
  • the optional vacuum dry is carried out by specific equipment capable to remove solvents by applying high vacuum in specific chamber in which the coated substrate is loaded.
  • step f) the intermediate product obtained in step e), if present, or step d), if step e) is not present, is cured.
  • the curing is usually effected by exposure to heat, e.g. by using a convection oven, hot plate or IR irradiation.
  • heat e.g. by using a convection oven, hot plate or IR irradiation.
  • thermal and UV cure process can be used.
  • the temperature used for curing usually does not exceed 300°C preferably does not exceed 250°C and most preferably does not exceed 150°C or does not exceed 80°C.
  • the curing time is usually 10 min to 5.0 hours, preferably 20 min to 3.0 hours, and most preferably 5 min to 1.0 hour.
  • the total fluorine content of the final thin film obtained after step f) is preferably is 0.2 to 15 wt.% based on the total weight of the thin film.
  • the thickness of the thin film after step f) is preferably 15.0 to 120 nm, more preferably 30 to 100 nm.
  • the film is preferably having a pencil hardness (PEHA) of at least 7H, preferably at least 8H, most preferably at least 9H.
  • PEHA pencil hardness
  • the film is preferably having an initial water contact angle of at least 1 10°, preferably at least 115°, most preferably at least 120°.
  • the film is preferably having a refractive index (at 632nm) below 1.50, preferably below 1.48, most preferably below 1.46.
  • the film is preferably having an RMS surface roughness of below 5.0nm, preferably below 3.5nm, most preferably below 2.5nm.
  • the film is preferably having an a * of between -0.2 - +0.2, preferably between -0.1 - +0.1 , most preferably between -0.05 - +0.05.
  • the film is preferably having an b * of between -0.2 - +0.2, preferably between -0.1 - +0.1 , most preferably between -0.05 - +0.05.
  • the film preferably delivers a transmission improvement of at least 0.5%, more preferably at least 0.75% and most preferably at least 1.0% when applied on gorilla glass substrate and comparison made to non-coated gorilla glass transmission.
  • the performance of the film after 5000 cycles is preferably less than 20 %, preferably less than 15 %, most preferably less than 10%.
  • the film preferably has a water contact angle after 100 000 cycle cotton cloth abrasion of at least 90°, more preferably at least 100° and most preferably at least 105° when applied onto a gorilla glass substrate.
  • the film preferably has a water contact angle after 8 000 cycle steel wool abrasion of at least 80 °, more preferably at least 90° and most preferably at least 100° when applied onto a gorilla glass substrate.
  • the film preferably has a water contact angle after 2500 cycle Minoan eraser abrasion of at least 90°, more preferably at least 100° and most preferably at least 105° when applied onto a gorilla glass substrate.
  • the film preferably has a water contact angle after 2 000 cycle steel wool abrasion of at least 85 °, more preferably at least 95° and most preferably at least 105° when applied onto a metal substrate.
  • the film preferably has a water contact angle after 3 000 cycle steel wool abrasion of at least 90 °, more preferably at least 100° and most preferably at least 105° when applied onto a sodalime glass substrate.
  • the film preferably has a water contact angle after 2 000 cycle steel wool abrasion of at least 80 °, more preferably at least 90° and most preferably at least 100° when applied onto a ceramic substrate.
  • A“sweat test” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 105° when applied on gorilla glass.
  • A“high temperature high humidity (85°C / 85%)” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 105° when applied on gorilla glass.
  • A“250°C temperature stability test” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 110° when applied on gorilla glass.
  • A“acid test” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 110° when applied on gorilla glass.
  • A“thermal cycling/shock (-40°C -> +85°C) test” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 110° when applied on gorilla glass.
  • An“UV stability test” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 1 10° when applied on gorilla glass.
  • A“200°C long term (6hours) high temperature stability” treated film preferably has a water contact angle after 5 000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 110° when applied on gorilla glass.
  • A“long term performance stability (over 6 months at room temperature)” tested film preferably has stability performance of abrasion of the film after 5000 cycles, measured as ratio of the contact angle after 5000 cycles to the initial contact angle, preferably less than 15 %, preferably less than 10 %, most preferably less than 8% when applied on gorilla glass.
  • the performance of the film after 5000 cycles measured as increase in the RMS surface roughness after 5000 cycles in comparison to the initial RMS surface roughness, is preferably less than 15 %, preferably less than 10 %, most preferably less than 5%.
  • the present invention is furthermore directed to an article, preferably an optically or electrically coated article, comprising the thin film obtainable by the process according to the present invention.
  • the article may be a touch panel display, such as a handheld touch panel display or other interactive touch screen device, a solar panel or a window or other glazing in general, mobile phone and computer metal casing and other metal surfaces.
  • a touch panel display such as a handheld touch panel display or other interactive touch screen device, a solar panel or a window or other glazing in general, mobile phone and computer metal casing and other metal surfaces.
  • Suitable materials for the articles which comprises the thin film obtainable by the process according to the invention include ceramics, glass, metals, natural and man-made stone, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene
  • copolymers such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), paints (such as those on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), wood and fibrous substrates (such as textile, leather, carpet, paper).
  • the material for the article is selected from ceramics, glass (example boroslicate glass, sodalime glass, aluminoslicate glass, or any other glass type), metals (such as aluminum, steel etc.), polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), natural and man-made stone, more preferably from metals, ceramics, glass and polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate).
  • ceramics glass
  • glass example boroslicate glass, sodalime glass, aluminoslicate glass, or any other glass type
  • metals such as aluminum, steel etc.
  • polymeric materials such as poly(
  • Thickness and shape of the article may vary case by case and can be flat, 2D or 3D shape.
  • the article can have chemical, physical and/or mechanical surface treatments before the thin film is applied to the article such as deposited onto the article.
  • example aluminum can be polished, anodized, colored or coated with other coating(s) prior to material deposition.
  • Glass can be non-tempered, thermally or chemically tempered and it can have different surface preparations including polishing, grinding, washing using various different surface treatment agents (alkaline or acidic).
  • the article can be either flat or can have a surface texture (example etched glass surface or anodized aluminum surface) in it or other layers on the article can provide the texturing/currugated surface or no surface texture in it.
  • a surface texture example etched glass surface or anodized aluminum surface
  • the surface can be textured by using etching [e.g. to produce anti-glare (AG) effect on glass] or by applying coating layer to provide the AG effect.
  • etching e.g. to produce anti-glare (AG) effect on glass
  • coating layer to provide the AG effect.
  • the thin film can be directly applied onto the article as such that at least one surface of the article is in direct contact with the thin film.
  • the thin film can also be applied onto an intermediate layer as such that the inner surface of the intermediate layer is in direct contact with at least one surface of the article. The thin film is then in direct contact with the outer surface of the intermediate layer.
  • the intermediate layer can have mechanical, physical, chemical or optical function in connection with the material coating layer.
  • the intermediate layer can be actual physical coating layer or can be a modification on molecular and or atomic level in the article in the area of the surface which is in direct contact with the intermediate layer.
  • Preferred variants and embodiments of the process of the present invention are also preferred variants and embodiments of the article according to the present invention.
  • the present invention is furthermore directed to a composition comprising a first precursor composition (FPC) and a second precursor composition (SPC), the first precursor composition (FPC) being a polymerized metal or metalloid compound according to formula (I)
  • M 1 is a metal or metalloid with a valence z
  • R 1 is each independently selected from a Ci to Cio organyl or organoheteryl group
  • R 2 is each independently selected from a Ci to C20 organyl, organoheteryl,
  • n 1 to z-1
  • m 1 to z-1
  • n+m is z whereby the polymerization is effected by at least partial hydrolysation of the M 1 (OR 1 )- moieties;
  • Preferred features of the process according to the present invention are also preferred features of the composition of the present invention.
  • This composition is surprisingly stable at room temperature and slightly elevated temperature (up to 40°C).
  • the composition usually has a shelf life, determined as described in the experimental part of, of at least 6 months.
  • the present invention is furthermore directed to a kit-of-parts comprising a first precursor composition (FPC) in a first vessel and a second precursor composition (SPC) in a second vessel, the first precursor composition (FPC) being a polymerized metal or metalloid compound according to formula (I)
  • M 1 is a metal or metalloid with a valence z
  • R 1 is each independently selected from a Ci to Cio organyl or organoheteryl group
  • R 2 is each independently selected from a Ci to C20 organyl, organoheteryl,
  • n 1 to z-1
  • m 1 to z-1
  • n+m is z whereby the polymerization is effected by at least partial hydrolysation of the M 1 (OR 1 )- moieties;
  • the present invention is furthermore directed to the use of the composition or the kit-of-parts according to the present invention for preparing a thin film on a substrate.
  • the present invention is furthermore directed to the use of the composition or the kit-of-parts according to the present invention for preparing an optical or electrical coating.
  • Figure 1 shows a cross-section of a coated substrate on top of which material coating layer has been directly deposited.
  • Figure 2 shows a cross-section of coated substrate in which the substrate surface has an intermediate layer deposited on top of the substrate prior deposition of the material coating layer onto the intermediate layer.
  • Figure 3 shows a typical sequence of the deposition process of the material layer on top of the substrate.
  • Figure 4 shows cross-section images of a substrate and the material coating layer.
  • Figure 5 shows a typical sequence of the deposition and patterning process of the material layer on top of the substrate.
  • the tool used the measure molecular weight is WATERS GPC (gel permeation
  • the tool used to determine the molecular weight is Mettler Toledo HB43 Halogen dryer/balance. Sample is weighted on aluminum dish/cup and measurement is performed using about 1 gram of material.
  • Material shelf life is determined by following material process/application result stability/repeatability as cured film.
  • the values monitored from cured film are film thickness and abrasion performance.
  • the film thickness is characterized by using Ellipsometer (UVISEL-VASE Horiba Jobin-Yvon). Measurements are performed using Gorilla Glass 4 and silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: ⁇ 1-0-0>, Resistivity: 1-30 ohm-crn, Thickness: Q75+/-25 pm, TTV: ⁇ 5 pm, Particle: ⁇ 20 @ 0.2 pm, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) as substrates.
  • Material film depositions are done by using spray coating, the material film is spray coated on pretreated (plasma) glass substrate (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2), followed by thermal cure example at 150°C for 60 min. Viscosity
  • the film thickness and refractive index are measured by using Ellipsometer (UVISEL-VASE Horiba Jobin-Yvon). Measurements are performed using Gorilla Glass 4 or silicon wafer (Diameter: 150mm, Type/Dopant: P/Bor, Orientation: ⁇ 1-0-0>, Resistivity: 1-30 ohmcm, Thickness: 675+/-25pm, TTV: ⁇ 5pm, Particle: ⁇ 20 @ 0,2pm, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) as substrates.
  • Ellipsometer UVISEL-VASE Horiba Jobin-Yvon
  • the material film is prepared on pretreated (plasma) glass substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2), followed by thermal cure example at 150°C for 60 min.
  • a spray tool Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2
  • spectrophotometer CM-3700A (SpectraMagic NX software). Measurements are performed using Gorilla Glass 4 as substrates.
  • the material film is prepared on pretreated (plasma) glass substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2), followed by thermal cure example at 150°C for 60 min.
  • Film is prepared on pretreated (plasma) glass or anodized aluminum substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminum).
  • a spray tool Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2
  • the pencil hardness is determined according to ASTM standard D3363-00 using a Elcometer pencil hardness tester.
  • Film is prepared on pretreated (plasma) glass or anodized aluminum substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass and ceramic) and at 80°C for 60 min (for anodized aluminum).
  • the static contact angle measurement is performed by optical tensiometer using distilled water, 4pl droplet size, three measurement points average is recorded as the measurement result value and Young- Laplace equation is used as the numerical method to describe the contour of the drop (Tool: Attension Theta optical tensiometer).
  • other liquids can be used in addition to water, such as di-iodomethane and hexadecane, to characterize the surface.
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass and ceramic) and at 80°C for 60 min (for anodized aluminium and other metal). Abrasion testing is carried out using Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed. (Tools: Taber linear abraser, 5750).
  • Abrasion test evaluation criteria Initial water contact angle, water contact angle measurement at 1000 cycle intervals (up to 8000 cycles) and visual inspection for surface damage / visual scratch inspection at 1000 cycle intervals (up to 8000 cycles). Water contact angle is measured according to water contact angle measurement method and visual inspection is done under microscope inspection and green and red light quality lamp inspection. In addition to steel wool, also Cotton Cloth and Minoan Eraser are used to test the abrasion performance.
  • Film is prepared on pretreated (plasma) glass or anodized aluminum substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminum).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • the adhesion is determined according to ASTM standard D3359-D9 using a Elcometer Cross-hatch tester and Elcometer tape test.
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • initial measurements are carried out for the coated and cured substrate: Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle. After the initial measurements, the sample substrate is immersed in boiling
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • initial measurements are carried out for the coated and cured substrate: Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle. After the initial measurements, the sample substrate is immersed for 72
  • the sweat solution contains: Pure water 100ml + NaCI 5g + 2Na2HP04 5g + 99% acetic acid 2ml.
  • the sample is tested for adhesion and the sample goes into 5000 cycle abrasion testing (Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed).
  • Abrasion test transmission, reflection, L * , a * , b * and water contact angle are characterized and comparison made to the initial values to see if criteria is passed. In case when substrate is anodized aluminium only adhesion and water contact angle are measured and initial and after abrasion test values are compared and performance verified.
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle After the initial measurements, the sample substrate is immersed for 24 hours in acid solution.
  • the acid solution contains: 1 mass
  • L * , a * , b * and water contact angle are characterized and comparison made to the initial values to see if criteria is passed. In case when substrate is anodized aluminium only adhesion and water contact angle are measured and initial and after abrasion test values are compared and performance verified.
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • initial measurements are carried out for the coated and cured substrate: Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle. After the initial measurements, the sample is placed in an environmental chamber
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • initial measurements are carried out for the coated and cured substrate: Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle. After the initial measurements, to run the High Temperature Test 1
  • the sample is placed in convection oven at 200°C for 6 days. After the High Temperature Test is completed the sample is tested for adhesion and the sample goes into 5000 cycle abrasion testing (Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed). After Abrasion test, transmission, reflection, L * , a * , b * and water contact angle are characterized and comparison made to the initial values to see if criteria is passed. In case when substrate is anodized aluminium only adhesion and water contact angle are measured and initial and after abrasion test values are compared and performance verified.
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • initial measurements are carried out for the coated and cured substrate: Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle. After the initial measurements, the sample is placed in to a
  • the test chamber follows a following temperature cycle going from - 40°C (kept for 10min) to +85°C (kept for 10min) and temperature cycled constantly between these two temperatures (10 seconds between temperature change) for 120 cycles in total.
  • the sample is tested for adhesion and the sample goes into 5000 cycle abrasion testing (Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed).
  • abrasion testing Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed.
  • transmission, reflection, L * , a * , b * and water contact angle are characterized and comparison made to the initial values to see if criteria is passed. In case when substrate is anodized aluminium only adhesion and water contact angle are measured and initial and after abrasion test values are compared and performance verified.
  • Film is prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2 ), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • Typical spray process Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm 2
  • thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium).
  • initial measurements are carried out for the coated and cured substrate: Adhesion, Transmission, Reflection, L * , a * , b * and water contact angle. After the initial measurements, the sample is placed in to UV St
  • the UV test chamber follows cycle where the samples gets first 4 hours of 0.77W/m A 2 UV exposure (at 60°C) and after this follows a 4 hour long 50°C condensing conditions and this is cycled 5 times for total of 40 hours.
  • the sample is tested for adhesion and the sample goes into 5000 cycle abrasion testing (Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed).
  • Abrasion test transmission, reflection, L * , a * , b * and water contact angle are characterized and comparison made to the initial values to see if criteria is passed. In case when substrate is anodized aluminium only adhesion and water contact angle are measured and initial and after abrasion test values are compared and performance verified.
  • Film is prepared on pretreated (plasma) gorilla glass by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min;
  • Atomization air pressure 5 kg/cm 2
  • thermal cure example 150°C for 60 min.
  • coated gorilla glass sample is kept at office desk and tested at 2 month, 4 month and 6 month measurement points. The sample is tested for adhesion and the sample goes into 5000 cycle abrasion testing (Bon Star steel wool #0000, 1 kg load, 1x1 cm head, 2 inch stroke, 60c/min speed). After Abrasion test, transmission, reflection, L * , a * , b * and water contact angle are characterized and comparison made to the initial values to see if criteria is passed.
  • Figure 1 shows a cross-section of a coated substrate 100 on top of which material coating layer 1 10 has been deposited.
  • the material coating layer 1 10 can be coated on both sides (double sided) of the substrate 100.
  • Figure 2 shows a cross-section of coated substrate 200 in which case the substrate surface has an intermediate layer 210 deposited on top of the substrate prior deposition of the material coating layer 220 on layer 210.
  • the intermediate layer 210 can have mechanical, physical, chemical or optical function in connection with the material coating layer 220.
  • the intermediate layer can be actual physical coating layer or can be a modification on molecular and or atomic level in the substrate 200 material at the very top surface.
  • the coating layer 210 can be a primer layer activating the substrate 200 surface to achieve good adhesion between the substrate 200 and material coating layer 220. It can be alternatively also a (patterned or non-patterned) coating layer providing example additional glass corrosion protection, diffusion barrier, conductive or semi-conductive coating layer or optical coating layer playing a role improving the optical properties of the total coating stack.
  • the coating layer 210 can be the actual material coating layer (in this case also additional optional coating layer between the susbtrate 200 and coating layer 210 can be applied) described in the invention and coating layer 220 can function as the additional surface treatment chemical, primer or a (patterned or non-patterned) coating layer providing example additional glass corrosion protection, diffusion barrier, conductive or semi-conductive coating layer and/or optical coating layer playing a role improving the optical properties of the total coating stack. Specifically it can also provide additional increase in the water contact angle and oil contact angle of the material coating layer 210 and total coating stack.
  • Step 3 shows a typical sequence of the deposition process of the material layer on top of the substrate.
  • Step 1 includes substrate preparation
  • Step 2 includes the coating process
  • Step 3 includes the coating curing to its final form.
  • Suitable substrates include ceramics, glass, metals, natural and man-made stone, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), paints (such as those on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), wood and fibrous substrates (such as textile, leather, carpet, paper).
  • polymeric materials such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate
  • paints such as those on acrylic resins
  • powder coatings such as polyurethane or hybrid powder coatings
  • wood and fibrous substrates such as textile, leather, carpet, paper.
  • the substrate is selected from ceramics, glass (example boroslicate glass, sodalime glass, aluminoslicate glass, or any other glass type), metals (such as aluminum, steel etc.), polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), natural and man-made stone, more preferably from metals, ceramics, glass and polymeric materials (such as
  • Thickness and shape of the substrate may vary case by case and can be flat, 2D or 3D shape.
  • the substrates can have chemical, physical and/or mechanical surface treatments prior to material deposition (and have intermediate layers deposited prior to actual coating material deposition).
  • example aluminum can be polished, anodized, colored or coated with other coating(s) prior to material deposition.
  • Glass can be non-tempered, thermally or chemically tempered and it can have different surface preparations including polishing, grinding, washing using various different surface treatment agents (alkaline or acidic).
  • the substrates can be either flat or can have a surface texture (example etched glass surface or anodized aluminum surface) in it or other layers on the substrate can provide the texturing/currugated surface or no surface texture in it.
  • the surface can be textured by using etching [e.g. to produce anti glare (AG) effect on glass] or by applying coating layer to provide the AG effect.
  • the material coating layer is applied by using a wet chemical coating processes, preferably with spin-on, dip, spray, bar, ink-jet, roll-to-roll, gravure, flexo-graphic, screen-printing, curtain, drip, roller, screen printing coating methods, a brush coating or by rubbing, extrusion coating and slot coating, combined slot+spin, more preferably by spray coating, slot coating, dip coating, spin coating, most preferably spray coating (to mention few typical liquid phase deposition methods but not limited to these).
  • a wet chemical coating processes preferably with spin-on, dip, spray, bar, ink-jet, roll-to-roll, gravure, flexo-graphic, screen-printing, curtain, drip, roller, screen printing coating methods, a brush coating or by rubbing, extrusion coating and slot coating, combined slot+spin, more preferably by spray coating, slot coating, dip coating, spin coating, most preferably spray coating (to mention few typical liquid phase deposition methods but not limited to these).
  • After the wet chemical coating step there is
  • Plasma pre-treatment (equipment brand: Creating-nano; model: CNT-ASP003RT)
  • Figure 4 show cross-section images of a substrate 400 and material coating layer 410.
  • patterning process nano-imprinting, embossing, roll-to- roll, gravure, flexo-graphic, roller, ink-jet, screen-printing, spray and or UV lithography is used as patterning process
  • form surface structures nano-scale or micro or millimeter scale
  • Figure 5 shows a typical sequence of the deposition and patterning process of the material layer 510 on top of the substrate 500.
  • Step 1 includes substrate preparation
  • Step 2 includes the coating process
  • Step 3 includes the patterning process of the material coating (this may include thermal and UV curing or combination of both)
  • Step 4 includes the coating curing for its final form.
  • Step 2 and Step 3 can be combined as a one single step depending on the deposition and patterning technique.
  • materials are provided which are suitable for produce films and structures.
  • the layers can be deposited on various substrate surfaces, such as glass, silicon, silicon nitride, different oxide coating layers, metals, ceramics and plastics.
  • the patterning of the thermally and/or irradiation sensitive material compositions can be performed via direct lithographic patterning, conventional lithographic masking and etching procedure, imprinting and embossing, but are not limited to these.
  • compositions can be used for making layers which are cured at relatively low processing temperatures, e.g. at a temperature of max 250 °C or even at temperature of 50 °C and in the range between these limits.
  • the material film and/or structures are capable of withstanding aggressive environmental conditions and has high mechanical durability, thermal stability and chemical stability, through which long-term stability of the anti smudge and easy-to-clean properties and antireflective properties is achieved and sustained.
  • the invention will be illustrated with the aid of a number of non-limiting working examples giving further details of the preparation of the above-discussed siloxane polymer coating compositions and of their use for producing coatings.
  • Solution 1 Tetraethoxysilane (63.84 g) and acetone (200g) was placed to the round bottom flask. 44.6 g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 178 g and it solid content was 14.45 %. Solution was further diluted to 10 % using 2-methoxy-propanol (79.21 grams).
  • Solution 2 Tetraethoxysilane (60.64g), 1 ,2-bistriethoxysilylethane (5.43 g) and acetone (200g) was placed to the round bottom flask. 45.26g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 178.66 g and it solid content was 17.20 %. Solution was further diluted to 10 % using 2-methoxy-propanol (128.59 g).
  • Solution 3 Tetraethoxysilane (60.64g), phenyltrimethoxysilane (2.73g) and acetone (200g) was placed to the round bottom flask. 43.60g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 176 g and it solid content was 16.44 %. Solution was further diluted to 10 % using 2-methoxy-propanol (1 13.34 g).
  • Solution 4 Tetraethoxysilane (60.64g), 3-glycidoxypropyltrimethoxysilane (3.62g) and acetone (200g) was placed to the round bottom flask. 43.60g of 0.1 M HNO 3 was added dropwise.
  • Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 171.05 g and it solid content was 18.46 %. Solution was further diluted to 10 % using 2-methoxy-propanol (144,70 g).
  • Example 5 Tetraethoxysilane (60.64g), methacryloxypropyltrimethoxysilane (3.80 g) and acetone (200g) was placed to the round bottom flask. 43.60g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 168.73 g and it solid content was 17.60 %. Solution was further diluted to 10 % using 2- methoxy-propanol (128.23 g).
  • Solution 6 Tetraethoxysilane (60.64g), methyltriethoxysilane (2.57g) and acetone (200g) was placed to the round bottom flask. 43.60g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 172.26 g and it solid content was 16.97 %. Solution was further diluted to 10 % using 2-methoxy-propanol (120.06 g).
  • Solution 7 Tetraethoxysilane (60.64g), Ethyltrimethoxysilane (2.08 g) and acetone (200g) was placed to the round bottom flask. 43.60g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 177 g and it solid content was 16.43 %. Solution was further diluted to 10 % using 2-methoxy-propanol (1 13.81 g).
  • Solution 8 Tetraethoxysilane (60.64g), phenylmethyldimethoxysilane (2.79g) and acetone (200g) was placed to the round bottom flask. 43.05g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 175.88 g and it solid content was 16,08 %. Solution was further diluted to 10 % using 2-methoxy-propanol (106.93 g).
  • Solution 9 Tetraethoxysilane (63.84g) and ethanol (75g) was placed to the round bottom flask. 44.16g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Finally, the solution was diluted to 10 % solid content.
  • Solution 10 Tetraethoxysilane (63.84g) and Novec 7100 (50g) and Acetone (50g) was placed to the round bottom flask. 44.16g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Finally, the solution was diluted to 10 % solid content.
  • Solution 1 1 Tetraethoxysilane (63.84g) and 2-propanol (130g) was placed to the round bottom flask. 44.16g of 0.1 M HNO 3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Solid content was 10.41 %. Solution was diluted down to 10 % by adding 9.6 g of 2-propanol. Solution was refluxed at 95°C for 1 hours and cooled down. Solution was refluxed at 95°C for 1 hours and cooled down. 2-propanol was removed by rotary evaporator and 2- methoxy-propanol was added. Finally, the solution was diluted to 10 % solid content.
  • Solution 12 Tetraethoxysilane (63.84g) and 2-propanol (1 10g) was placed to the round bottom flask. 66.24g of 0.1 M HNO3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Solid content was 10.28 %. Solution was diluted down to 10 % by adding 6.54 g of 2-propanol.
  • Solution 13 Tetraethoxysilane (63.84g) and Acetone (200g) was placed to the round bottom flask. 44.16g of 0.1 M HNO3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. 200g of 2-methoxyethanol was added and solvent exchange from acetone to 2- methoxyethanol was started using reduced pressure. Solid content was 16.45 %. Solution was diluted down to 10 % by adding 1 13.7 g of 2-methoxyethanol.
  • Solution 14 Tetraethoxysilane (63.84g) and 2-propanol (200g) was placed to the round bottom flask. 44.16g of 0.1 M HNO3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. 200g of 2-propanol was added and solvent exchange from 2-propanol to 2- propanol was started using reduced pressure. Solid content was 13.9 %. Solution was diluted down to 10 % by adding 69.1 g of 2-propanol.
  • Solution 15 Tetraethoxysilane (63.84g) and tetrahydrofuran (200g) was placed to the round bottom flask. 44.16g of 0.1 M HNO3 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. 200g of 2-methoxy-1 -propanol was added and solvent exchange from tetrahydrofuran to 2-methoxy-1 -propanol was started using reduced pressure. Solid content was 14.94 %. Solution was diluted down to 10 % by adding 93.26 g of 2-methoxy-1 -propanol
  • Solution 16 Tetraethoxysilane (63.84g) and 2-methoxy-1 -propanol (130g) was placed to the round bottom flask. 44.16g of 0.1 M HNO3 was added dropwise. Solution was refluxed at 105°C for 1 hours and cooled down. Solid content was 1 1 .35 %. Solution was diluted down to 10 % by adding 31 .64 g of 2-methoxy-1 -propanol.
  • Solution 18 Tetraethoxysilane (50.64g), 1 ,2-bistriethoxysilylethane (5.43 g) and
  • perfluorododecyl-1 H,1 H,2H,2H-triethoxysilane (1.5g), perfluorotetradecyl-1 H,1 H,2H,2H- triethoxysilane (2.4g) and acetone (200g) was placed to the round bottom flask. 43.27g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down.
  • Acetone was removed by rotary evaporator and 2-methoxy-propanol was added.
  • Solution amount achieved was 178.66 g and it solid content was 15.20 %.
  • Solution was further diluted to 10 % using 2-methoxy-propanol (123.59 g).
  • Solution 19 Tetraethoxysilane (50.64g), [(4-trifluoromethyl)-2, 3,5,6- tetrafluorophenyl]triethoxysilane (2.1 g) and acetone (200g) was placed to the round bottom flask. 41 33g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 178.66 g and it solid content was 14.20 %. Solution was further diluted to 10 % using 2-methoxy-propanol (1 14.59 g).
  • trimethoxy(3,3,3-trifluoropropyl)silane (1 .9g) and acetone (200g) was placed to the round bottom flask. 41 90g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 178.66 g and it solid content was 15.20 %. Solution was further diluted to 10 % using 2-methoxy-propanol (1 10.59 g).
  • Solution 21 Tetraethoxysilane (50.64g), 1 H, 1 H, 2H, 2H- perfluorodecyltrimethoxysilane (2.6g) and acetone (200g) was placed to the round bottom flask. 44.26g of 0.1 M HN03 was added dropwise. Solution was refluxed at 95°C for 1 hours and cooled down. Acetone was removed by rotary evaporator and 2-methoxy-propanol was added. Solution amount achieved was 178.66 g and it solid content was 18.20 %. Solution was further diluted to 10 % using 2- methoxy-propanol (132.59 g).
  • Spray set-up and spray parameter
  • HVLP spray gun with 0 0.3-0.5 mm nozzle; Typical settings: Scan Speed (300-1200mm/s),
  • Spray set-up can be such that substrate is moving (10mm - 100 mm/s), while spray head or spray heads are moving/scanning e.g.
  • the substrate can be also mounted in so called spindle spray set-up, where the substrate is spinning (50-1000 rpm/min) while spray head or spray heads are stationary or optionally also moving relative to the substrate.
  • Spindle spray set-up can be beneficial to use especially for deposition of 3D objects.
  • Step 1 Liquid alkaline or acidic glass clean solution; non-foaming cleaning agent to be used in glass clean machinery; Step 2: Dl water clean step in glass clean machinery; Step 3: Plasma/Corona treatment (If possible make water contact angle check ⁇ 5°, as quality check) (In case of glass either a liquid clean and/or plasma clean steps can be used); Step 4: Spray Process; Optimize spray parameters to target cured film thickness of 40-100 nm; handle substrates with care not to damage wet coating when transfering to thermal cure; Step 5: Curing temperature 80-250°C; Curing time 30-60 minutes; no special atmosphere
  • the line contains the pre-clean (alkaline clean+DI+plasma), optional additional coating process followed by the material spray coat deposition and finally thermal curing step also integrated on same in-line conveyor.
  • the conveyor speed can typically vary e.g. from 0.2m/min to 0.8m/min.
  • the spray head scan speed can typically vary e.g. from 100mm/s to 1200mm/s depending on how many spray heads are installed accross the conveyor, so full surface area can be cover by the spray heads.
  • the spray head distance from the substrate surface can vary from 50mm to 200mm. Typical atomization pressure used in between 1.5 - 4 Bar. Typical material feed pressure is 0.2 - 2.0 bar. Final cure is done at 80°C - 150°C.
  • Line speed in the thermal cure conveyor can be example 0.2 - 0.8 m/min.
  • the film thickness, coating uniformity and coating quality can be optimized by tuning the material composition and formulation and deposition parameters.
  • the materials according to this invention allow specifically very high tuneability in compositional and formulation tuning to suit wide variety of liquidphase deposition techniques to be used.
  • spray coating is described as the coating method of choice.
  • Films are prepared on pretreated (plasma) glass, anodized aluminum or ceramic substrate by using a spray tool.
  • plasma pretreated glass
  • sodalime glass following sample clean process is used:
  • alkaline clean (RBS or similar alkaline clean solution PH 10); b) Dl-water; followed by c) plasma clean.
  • Gap 100 mm
  • Atomization air pressure 5 kg/cm 2 ; Spray process is followed by a thermal cure example at 150°C for 60 min (for glass and ceramic) and at 80°C for 60 min (for anodized aluminium and other metal). Thermal cure is done in oven or on conveyor. Samples are characterized according to measuring methods defined earlier and data summarized on the various synthesis examples in the following tables.
  • Table 1 Cured film properties of Examples 1 A - 8A on Gorilla glass.
  • Table 2 Cured film properties of Examples 9A - 22Z on Gorilla glass.
  • Spray process Scan Speed (300mm/s), Pitch (50mm), Gap (100mm), Atomization pressure (5 Kg/cm2) and Flow rate (10ml/min)
  • Table 8 Abrasion resistance of material example 14C on flat and textured sodalime glass.
  • Table 10 Shelf-life data summary for material example 1A on Gorilla glass.
  • the invention provides following key features:
  • ⁇ Suitable for glass, metal, AG or AR and other surfaces; the invention provides wide choice of substrate surfaces on which it delivers superior performance.
  • Example the conventional approaches cannot deliver and meet performance on Sodalime etched anti-glare glass or metal surface without primer layer.
  • the samples according to the invention can deliver also superior shelf-life stability for the coating composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un film mince sur un substrat dans lequel une première composition de précurseur (FPC) et une seconde composition de précurseur (SPC) sont combinées, une couche mince des première composition de précurseur (FPC) et seconde composition de précurseur (SPC) combinées est formée sur un substrat et la couche mince est durcie, un article comprenant ladite couche mince, une composition comprenant ladite première composition de précurseur (FPC) et ladite seconde composition de précurseur (SPC), un kit de parties comprenant ladite première composition de précurseur (FPC) et ladite seconde composition de précurseur (SPC)) dans deux récipients et l'utilisation de ladite composition ou dudit kit de parties pour la préparation d'un film mince sur un substrat et pour la préparation d'un revêtement optique ou électrique.
PCT/EP2019/080795 2018-11-13 2019-11-11 Revêtement facile à nettoyer WO2020099290A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP19798104.6A EP3880371A1 (fr) 2018-11-13 2019-11-11 Revêtement facile à nettoyer
CN201980074374.9A CN113015581A (zh) 2018-11-13 2019-11-11 易清洁的涂层
KR1020217017637A KR20210090670A (ko) 2018-11-13 2019-11-11 세정이 용이한 코팅
US17/293,665 US20220010170A1 (en) 2018-11-13 2019-11-11 Easy to clean coating
JP2021525814A JP2022507316A (ja) 2018-11-13 2019-11-11 洗浄が容易なコーティング

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EP18205971 2018-11-13
EP18205971.7 2018-11-13

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CN (1) CN113015581A (fr)
TW (1) TW202035596A (fr)
WO (1) WO2020099290A1 (fr)

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WO2023198748A1 (fr) 2022-04-14 2023-10-19 Optitune Oy Procede de preparation d'un revetement resistant à l'abrasion
WO2023198743A1 (fr) 2022-04-14 2023-10-19 Optitune Oy Revêtement dur de polysiloxane multicouche flexible
WO2023198746A1 (fr) 2022-04-14 2023-10-19 Optitune Oy Revêtement dur de polysiloxane multicouche souple

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WO2012064653A1 (fr) * 2010-11-10 2012-05-18 3M Innovative Properties Company Procédé de traitement de surface, composition à utiliser dans ce procédé et article traité
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WO2023198748A1 (fr) 2022-04-14 2023-10-19 Optitune Oy Procede de preparation d'un revetement resistant à l'abrasion
WO2023198743A1 (fr) 2022-04-14 2023-10-19 Optitune Oy Revêtement dur de polysiloxane multicouche flexible
WO2023198746A1 (fr) 2022-04-14 2023-10-19 Optitune Oy Revêtement dur de polysiloxane multicouche souple

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CN113015581A (zh) 2021-06-22
KR20210090670A (ko) 2021-07-20
US20220010170A1 (en) 2022-01-13
TW202035596A (zh) 2020-10-01
EP3880371A1 (fr) 2021-09-22
JP2022507316A (ja) 2022-01-18

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